Contrasting reactivity behaviour of the RuHCl(CO)(PNP)] complex with electrophilic reagents XOTf (X = H, CH3, Me3Si)

A new ruthenium pincer complex RuHCl(CO)(PNP)] (PNP = PhCH2N(CH2CH2PPh2)(2)) (1) was synthesized and characterized. The reactivity of complex 1 with electrophilic reagents XOTf (X = H, CH3, and Me3Si; OTf = CF3SO3) was studied by variable temperature NMR spectroscopy with an aim to observe and characterize sigma complexes of type Ru(eta(2)-HX)Cl(CO)(PNP)]OTf] (X = H (2), CH3 (3), Me3Si (4)). Reaction of complex 1 with HOTf resulted in the formation of the dihydrogen complex, Ru(eta(2)-H-2)Cl(CO)(PNP)OTf] (2). On the other hand, the reaction between complex 1 and MeOTf and Me3SiOTf resulted in the direct elimination of MeCl and Me3SiCl via a S(N)2 type of reaction without the intermediacy of the respective sigma complexes 3 and 4. This contrasting reactivity behaviour has been rationalized taking into consideration the approach of the relatively bulky electrophites CH3+ and Me3Si+ onto the hydride moiety of the ruthenium fragment, which is sterically hindered.

Newton-based stochastic optimization using q-Gaussian smoothed functional algorithms

We present the first q-Gaussian smoothed functional (SF) estimator of the Hessian and the first Newton-based stochastic optimization algorithm that estimates both the Hessian and the gradient of the objective function using q-Gaussian perturbations. Our algorithm requires only two system simulations (regardless of the parameter dimension) and estimates both the gradient and the Hessian at each update epoch using these. We also present a proof of convergence of the proposed algorithm. In a related recent work (Ghoshdastidar, Dukkipati, & Bhatnagar, 2014), we presented gradient SF algorithms based on the q-Gaussian perturbations. Our work extends prior work on SF algorithms by generalizing the class of perturbation distributions as most distributions reported in the literature for which SF algorithms are known to work turn out to be special cases of the q-Gaussian distribution. Besides studying the convergence properties of our algorithm analytically, we also show the results of numerical simulations on a model of a queuing network, that illustrate the significance of the proposed method. In particular, we observe that our algorithm performs better in most cases, over a wide range of q-values, in comparison to Newton SF algorithms with the Gaussian and Cauchy perturbations, as well as the gradient q-Gaussian SF algorithms. (C) 2014 Elsevier Ltd. All rights reserved.

Relaxor behaviour in BaBi4Ti4O15 ceramics fabricated using the powders obtained by mechanochemically assisted synthesis route

Mechanochemically activated reactants were found to facilitate the synthesis of fine powders comprising 200-400 nm range crystallites of BaBi4Ti4O15 at a significantly lower temperature (700 A degrees C) than that of solid-state reaction route. Reactants (CaCO3, Bi2O3 and TiO2) in stoichiometric ratio were ball milled for 48 h to obtain homogeneous mixture. The evolution of the BaBi4Ti4O15 phase was systematically followed using X-ray powder diffraction (XRD) technique. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were employed to probe its structural and microstructural details. The electron diffraction studies established the presence of correlated octahedral rotations and associated long-range polar ordering. High-resolution TEM imaging nevertheless revealed structural inhomogeneities leading to intergrowth defects. Dense BaBi4Ti4O15 ceramics with an average grain size of 0.9 mu m were fabricated using mechanochemically assisted synthesized powders at relatively low temperature (1000 A degrees C). The effect of grain size on the dielectric and relaxor behaviour of BaBi4Ti4O15 ceramics was investigated. Fine-grained ceramics (average grain size similar to 0.9 mu m) showed higher diffusion in phase transition, lower temperature of phase transition, lower Vogel-Fulcher freezing temperature and higher activation energy for the polarization reversal than those for coarse-grained ceramics (average grain size similar to 7 mu m) fabricated via the conventional solid-state reaction route.

Surface modification of textured silicon and its wetting behaviour

Textured silicon (Si) substrate were prepared using various texturing methods both chemical and physical and their water contact angle, surface topography and Raman spectra were studied and investigated. The effect of plasma and chemical treatment on micro/nanostructure and roughness of the surface with and without deposition of Octadecyltrichlorosilane (ODTS, Cl3Si (CH3)(17)), self-assembled monolayer (SAM) is investigated for achieving higher water contact angle (theta(c)). The importance of synergism of texturing with deposition of ODTS SAM in preparing superhydrophobic silicon surfaces has been discussed. It is shown that superhydrophobic silicon surfaces can be achieved on silicon surfaces by coating with ODTS, irrespective of whether it is textured or not, polished or unpolished, provided a chemical treatment is given to the surface prior to the ODTS coating.

Iterated stochastic filters with additive updates for dynamic system identification: Annealing-type iterations and the filter bank

A nonlinear stochastic filtering scheme based on a Gaussian sum representation of the filtering density and an annealing-type iterative update, which is additive and uses an artificial diffusion parameter, is proposed. The additive nature of the update relieves the problem of weight collapse often encountered with filters employing weighted particle based empirical approximation to the filtering density. The proposed Monte Carlo filter bank conforms in structure to the parent nonlinear filtering (Kushner-Stratonovich) equation and possesses excellent mixing properties enabling adequate exploration of the phase space of the state vector. The performance of the filter bank, presently assessed against a few carefully chosen numerical examples, provide ample evidence of its remarkable performance in terms of filter convergence and estimation accuracy vis-a-vis most other competing filters especially in higher dimensional dynamic system identification problems including cases that may demand estimating relatively minor variations in the parameter values from their reference states. (C) 2014 Elsevier Ltd. All rights reserved.

Single-ion magnet behaviour of heptacoordinated Fe(II) complexes: on the importance of supramolecular organization

Supramolecular organization of a metal complex may significantly contribute to the magnetization dynamics of mononuclear SMMs. This is illustrated for a heptacoordinated Fe(II) complex with rather moderate Ising-type anisotropy for which a slow magnetization relaxation with significant energy barrier was reached when this complex was properly organized in the crystal lattice. Incidentally, it is the first example of single-ion magnet behaviour of Fe(II) in a pentagonal bipyramid surrounding.

Experimental studies on the influence of intermediate principal stress and inclination on the mechanical behaviour of angular sands

A comprehensive experimental study has been made on angular sand to investigate various aspects of mechanical behavior. A hollow cylinder torsion testing apparatus is used in this program to apply a range of stress conditions on this angular quartzitic fine sand under monotonic drained shear. The effect of the magnitude and inclination of the principal stresses on an element of sand is studied through these experiments. This magnitude and inclination of the principal stresses are presented as an ``ensemble measure of fabric in sands''. This ensemble measure of fabric in the sands evolves through the shearing process, and reaches the final state, which indeed has a unique fabric. The sand shows significant variation in strength with changing inclination of the principal stresses. The locus of the final stress state in principal stress space is also mapped from these series of experiments. Additional aspects of non-coaxiality, a benchmarking exercise with a few constitutive models is presented here. This experimental approach albeit indirect shows that a unique state which is dependent on the fabric, density and confining stress exists. This suite of experiments provides a well-controlled data set for a clear understanding on the mechanical behavior of sands.

Deformation behaviour of Rheocast A356 Al alloy at microlevel considering approximated RVEs

A micromechanical approach is considered here to predict the deformation behaviour of Rheocast A356 (Al-Si-Mg) alloy. Two representative volume elements (RVEs) are modelled in the finite element (FE) framework. Two dimensional approximated microstructures are generated assuming elliptic grains, based on the grain size, shape factor and area fraction of the primary Al phase of the said alloy at different processing condition. Plastic instability is shown using stress and strain distribution between the Al rich primary and Si rich eutectic phases under different boundary conditions. Boundary conditions are applied on the approximated RVEs in such a manner, so that they represent the real life situation depending on their position on a cylindrical tensile test sample. FE analysis is carried out using commercial finite element code ABAQUS without specifying any damage or failure criteria. Micro-level in-homogeneity leads to incompatible deformation between the constituent phases of the rheocast alloy and steers plastic strain localisation. Plastic stain localised regions within the RVEs are predicted as the favourable sites for void nucleation. Subsequent growth of nucleated voids leads to final failure of the materials under investigation.

Correlation of microstructure and creep behaviour of MRI230D Mg alloy developed by two different casting technologies

The relationship between the as-cast microstructure and creep behaviour of the heat-resistant MRI230D Mg alloy produced by two different casting technologies is investigated. The alloy in both ingot-casting (IC) and high pressure die-casting (HPDC) conditions consists of alpha-Mg, 06 ((Mg,AI)(2)Ca), Al-Mn and Sn-Mg-Ca rich phases. However, the HPDC alloy resulted in relatively finer grain size and higher volume fraction of finer, denser network of eutectic C36 phase in the as-cast microstructure as compared to that of the IC alloy. The superior creep resistance exhibited by the HPDC alloy at all the stress levels and temperatures employed in the present investigation was attributed to the more effective dispersion strengthening effect caused by the presence of finer and denser network of the C36 phase. The increased amount of the eutectic C36 phase was the only change observed in the microstructures of both alloys following creep tests. (C) 2015 Elsevier B.V. All rights reserved.